Process for the synthesis of arylamines from the reaction of an aromatic compound with ammonia or a metal amide

Abstract

A catalytic process for the synthesis of aromatic primary amines, reagent compositions for effecting the process, and transition metal complexes useful in the process, are provided.

1. A process for preparing an aromatic primary amine, said aromatic primary amine comprising an amino group attached to an aromatic ring, said process comprising reacting:
 (a) an arylating agent comprising a leaving group attached to an aromatic ring; and 
 (b) an ammoniating agent selected from the group consisting of:
 (i) ammonia; and 
 (ii) a metal amide; 
 
 
       in a composition comprising a complex comprising:
 (a) a Group VIII metal atom or ion; and 
 (b) a ligand, wherein the ligand is a compound of formula I: 
 
       
         
           
           
               
               
           
         
       
       wherein:
 R 1  and R 2  are independently selected from the group consisting of (C 1 -C 12 )alkyl, (C 1 -C 12 )heteroalkyl, and optionally substituted aromatic rings, or —PR 1 R 2  is a radical of the formula II: 
 
       
         
           
           
               
               
           
         
         wherein α and β are optionally substituted aromatic rings; 
         R 3  and R 4  are independently selected from the group consisting of (C 1 -C 12 )alkyl, (C 1 -C 12 )heteroalkyl, and optionally substituted aromatic rings, or —PR 3 R 4  is a radical of the formula II; 
         R 5  is selected from the group consisting of hydrogen, (C 1 -C 8 )alkyl, (C 1 -C 8 )heteroalkyl and optionally substituted aromatic rings, 
         each R 6  is independently selected from the group consisting of hydrogen, and (C 1 -C 4 )alkyl; 
         wherein each of said optionally substituted aromatic rings is either unsubstituted or substituted at any substitutable position with one or more substituents independently selected from the group consisting of (C 1 -C 4 )alkyl, (C 1 -C 4 )heteroalkyl, (C 1 -C 3 ) fluorinated alkyl, —OR 7 , —SR 7 , and NR 7   2 ; 
         each R 7  is independently selected from the group consisting of (C 1 -C 4 )alkyl and (C 1 -C 4 )heteroalkyl, or, within any occurrence of NR 7   2 , independently of any other occurrence of NR 7   2  the two R 7  groups in combination form (C 4 -C 8 )alkylene or (C 4 -C 8 )heteroalkylene; 
         or any one occurrence of R 6 , or any one substitutable position of any one of the groups R 1 , R 2 , R 3 , R 4 , R 5  and R 7 , is a point of attachment, directly or via a tethering group, to a polymer or a solid phase support; 
         provided that when the ammoniating agent is ammonia, the composition comprising the complex further comprises a base; 
         whereby the leaving group of the arylating agent is substituted by an amino group to form the aromatic primary amine. 
       
     
     
       2. A process according to  claim 1 , wherein the Group VIII metal is selected from the group consisting of nickel, palladium and platinum. 
     
     
       3. A process according to  claim 1 , wherein the Group VIII metal is palladium. 
     
     
       4. A process according to  claim 3 , wherein the leaving group is a halogen selected from the group consisting of chloride, bromide and iodide. 
     
     
       5. A process according to  claim 3 , wherein the ammoniating agent is ammonia. 
     
     
       6. A process according to  claim 5 , wherein the base is selected from the group consisting of alkali metal alkoxides, carbonates, and phosphates. 
     
     
       7. A process according to  claim 6 , wherein the base is selected from the group consisting of sodium t-butoxide, cesium carbonate, and tribasic potassium phosphate. 
     
     
       8. A process according to  claim 6 , wherein the base is sodium t-butoxide. 
     
     
       9. A process according to  claim 3 , wherein the ammoniating agent is a metal amide. 
     
     
       10. A process according to  claim 9 , wherein the metal amide is an alkali metal amide. 
     
     
       11. A process according to  claim 10 , wherein the composition further comprises a zinc halide. 
     
     
       12. A process according to  claim 9 , wherein the alkali metal amide is lithium amide. 
     
     
       13. A process according to  claim 12 , wherein the composition further comprises zinc chloride. 
     
     
       14. A process according to  claim 3 , wherein R 6  is other than hydrogen at one or fewer occurrences. 
     
     
       15. A process according to  claim 14 , wherein each R 6  is hydrogen. 
     
     
       16. A process according to  claim 14 , wherein R 5  is hydrogen or methyl. 
     
     
       17. A process according to  claim 15 , wherein R 5  is methyl. 
     
     
       18. A process according to  claim 14 , wherein each of R 3  and R 4  is independently secondary or tertiary alkyl. 
     
     
       19. A process according to  claim 17 , wherein each of R 3  and R 4  is independently secondary or tertiary alkyl. 
     
     
       20. A process according to  claim 19 , wherein each of R 3  and R 4  is tertiary alkyl. 
     
     
       21. A process according to  claim 20 , wherein each of R 3  and R 4  is t-butyl. 
     
     
       22. A process according to  claim 3 , wherein the compound according to formula I is selected from the group consisting of 1-[2-(bis(3,5-dimethyl-4-methoxyphenyl)phosphino)ferrocenyl]ethyldicyclohexylphosphine, 1-[2-(bis(4-trifluoromethylphenyl)phosphino)ferrocenyl]ethyl-di-t-butylphosphine; 1-[2-(di(3,5-bis-trifluoromethylphenyl)phosphino)-ferrocenyl]ethyldi(3,5-dimethylphenyl)phosphine; 1-[2-(di(3,5-bis-trifluoromethylphenyl) phosphino)ferrocenyl]ethyldicyclohexylphosphine; 1-[2-(di-(3,5-dimethylphenyl)phosphino)ferrocenyl]ethylbis(3,5-dimethylphenyl)phosphine; 1-[2-(di-2-furylphosphino)ferrocenyl]ethyldi-3,5-xylyl phosphine; 1-[2-(dicyclohexylphosphino)ferrocenyl]-ethyldicyclohexylphosphine; 1-[2-(dicyclohexylphosphino)ferrocenyl]-ethyldiphenylphosphine; 1-[2-(dicyclohexylphosphino)ferrocenyl]ethyldi-t-butylphosphine; 1-[2-(diphenylphosphino)ferrocenyl]ethyldi(3 ,5 -dimethylphenyl)phosphine; 1-[2-(diphenylphosphino)ferrocenyl]-ethyldicyclohexylphosphine; 1-[2-(diphenylphosphino)ferrocenyl]-ethyldicyclohexylphosphine; 1-[2-(diphenylphosphino)ferrocenyl]-ethyldiphenylphosphine; 1-[2-(diphenylphosphino)fenocenyl]ethyldi-t-butylphosphine; 1-[2-(di-p-tolylphosphino)ferrocenyl]-ethyldicyclohexylphosphine; 1-[2-(di-t-butylphosphino)ferrocenyl]-ethyldiphenylphosphine.; (R)-1-[(S)-2-(bis(3,5-dimethyl-4-methoxyphenyl)phosphino)ferrocenyl]ethyldicyclohexylphosphine; (R)-1-[(S)-2-(bis(4-trifluoromethylphenyl)phosphino)ferrocenyl]ethyl-di-t-butylphosphine; (R)-1-[(S)-2-(di(3,5-bis-trifluoromethylphenyl)-phosphino)ferrocenyl]ethyldi(3,5-dimethylphenyl)phosphine; (R)-1-[(S)-2-(di(3,5-bis-trifluoromethylphenyl)phosphino)ferrocenyl]-ethyldicyclohexylphosphine; (R)-1-[(S)-2-(di-(3,5-dimethylphenyl)-phosphino)ferrocenyl]ethylbis(3,5-dimethylphenyl)phosphine; (R)-1-[(S)-2-(di-2-furylphosphino)ferrocenyl]ethyldi-3,5-xylyl phosphine; (R)-1-[(S)-2-(dicyclohexylphosphino)ferrocenyl]ethyldicyclohexylphosphine; (R)-1-[(S)-2-(dicyclohexylphosphino)ferrocenyl]ethyldiphenylphosphine; (R)-1-[(S)-2-(dicyclohexylphosphino)ferrocenyl]ethyldi-t-butylphosphine; (R)-1-[(S)-2-(diphenylphosphino)ferrocenyl]ethyldi(3,5-dimethylphenyl)-phosphine; (R)-1-[(S)-2-(diphenylphosphino)ferrocenyl]-ethyldicyclohexylphosphine; (R)-1-[(S)-2-(diphenylphosphino)ferrocenyl]-ethyldicyclohexylphosphine; (R)-1-[(S)-2-(diphenylphosphino)ferrocenyl]-ethyldiphenylphosphine; (R)-1-[(S)-2-(diphenylphosphino)ferrocenyl]-ethyldi-t-butylphosphine; (R)-1-[(S)-2-(di-p-tolylphosphino)ferrocenyl]-ethyldicyclohexylphosphine; (R)-1-[(S)-2-(di-t-butylphosphino)-ferrocenyl]ethyldiphenylphosphine; (S)-1-[(R)-2-(bis(3,5-dimethyl-4-methoxyphenyl)phosphino)ferrocenyl]ethyldicyclohexylphosphine; (S)-1-[(R)-2-(bis(4-trifluoromethylphenyl)phosphino)ferrocenyl]ethyl-di-t-butylphosphine; (S)-1-[(R)-2-(di(3,5-bis-trifluoromethylphenyl)-phosphino)ferrocenyl]ethyldi(3,5-dimethylphenyl)phosphine; (S)-1-[(R)-2-(di(3,5-bis-trifluoromethylphenyl)phosphino)ferrocenyl]-ethyldicyclohexylphosphine; (S)-1-[(R)-2-(di-(3,5-dimethylphenyl)-phosphino)ferrocenyl]ethylbis(3,5-dimethylphenyl)phosphine; (S)-1-[(R)-2-(di-2-furylphosphino)ferrocenyl]ethyldi-3,5-xylyl phosphine; (S)-1-[(R)-2-(dicyclohexylphosphino)ferrocenyl]ethyldicyclohexylphosphine; (S)-1-[(R)-2-(dicyclohexylphosphino)ferrocenyl]ethyldiphenylphosphine; (S)-1-[(R)-2-(dicyclohexylphosphino)ferrocenyl]ethyldi-t-butylphosphine; (S)-1-[(R)-2-(diphenylphosphino)ferrocenyl]ethyldi(3,5-dimethylphenyl)-phosphine; (S)-1-[(R)-2-(diphenylphosphino)ferrocenyl]-ethyldicyclohexylphosphine; (S)-1-[(R)-2-(diphenylphosphino)ferrocenyl]-ethyldicyclohexylphosphine; (S)-1-[(R)-2-(diphenylphosphino)ferrocenyl]-ethyldiphenylphosphine; (S)-1-[(R)-2-(diphenylphosphino)ferrocenyl]-ethyldi-t-butylphosphine; (S)-1-[(R)-2-(di-p-tolylphosphino)ferrocenyl]-ethyldicyclohexylphosphine; and (S)-1-[(R)-2-(di-t-butylphosphino)-ferrocenyl]ethyldiphenylphosphine. 
     
     
       23. A process according to  claim 3 , wherein the compound of formula I is selected from the group consisting of [2-(bis(3,5-dimethyl-4-methoxyphenyl)phosphino)ferrocenyl]methyldicyclohexylphosphine, [2-(bis(4-trifluoromethylphenyl)phosphino)ferrocenyl]methyl-di-t-butylphosphine; [2-(di(3,5-bis-trifluoromethylphenyl)phosphino)-ferrocenyl]methyldi(3,5-dimethylphenyl)phosphine; [2-(di(3,5-bis-trifluoromethylphenyephosphino)ferrocenyl]-methyldicyclohexylphosphine; [2-(di-(3 ,5-dimethylphenyl)phosphino)-ferrocenyl]methylbis(3,5-dimethylphenyl)phosphine; [2-(di-2-furylphosphino)ferrocenyl]ethyldi-3,5-xylyl phosphine; [2-(dicyclohexylphosphino)ferrocenyl]methyldicyclohexyphosphine; [2-(dicyclohexylphosphino)ferrocenyl]methyldiphenylphosphine; [2-(dicyclohexylphosphino)ferrocenyl]methyldi-t-butylphosphine; [2-(diphenylphosphino)ferrocenyl]methyldi(3,5-dimethylphenyl)phosphine; [2-(diphenylphosphino)ferrocenyl]methyldicyclohexylphosphine; [2-(diphenylphosphino)ferrocenyl]methyldicyclohexylphosphine; [2-(diphenylphosphino)ferrocenyl]methyldiphenylphosphine; [2-(diphenylphosphino)ferrocenyl]methyldi-t-butylphosphine; [2-(di-p-tolylphosphino)ferrocenyl]methyldicyclohexylphosphine; [2-(di-t-butylphosphino)ferrocenyl]methyldiphenylphosphine.; [(S)-2-(bis(3,5-dimethyl-4-methoxyphenyl)phosphino)ferrocenyl]-methyldicyclohexylphosphine; [(S)-2-(bis(4-trifluoromethylphenyl)-phosphino)ferrocenyl]methyl-di-t-butylphosphine; [(S)-2-(di(3,5-bis-trifluoromethylphenyl)phosphino)ferrocenyl]methyldi(3,5-dimethylphenyl)phosphine; [(S)-2-(di(3,5-bis-trifluoromethylphenyl)-phosphino)ferrocenyl]methyldicyclohexylphosphine; [(S)-2-(di-(3,5-dimethylphenyl)phosphino)ferrocenyl]methylbis(3,5-dimethylphenyl)-phosphine; [(S)-2-(di-2-furylphosphino)ferrocenyl]methyldi-3,5-xylyl phosphine; [(S)-2-(dicyclohexylphosphino)ferrocenyl]-methyldicyclohexylphosphine; [(S)-2-(dicyclohexylphosphino)ferrocenyl]-methyldiphenylphosphine; [(S)-2-(dicyclohexylphosphino)ferrocenyl]-methyldi-t-butylphosphine; [(S)-2-(diphenylphosphino)ferrocenyl]-methyldi(3,5-dimethylphenyl)phosphine; [(S)-2-(diphenylphosphino)-ferrocenyl]methyldicyclohexylphosphine; [(S)-2-(diphenylphosphino)-ferrocenyl]methyldicyclohexylphosphine; [(S)-2-(diphenylphosphino)-ferrocenyl]methyldiphenylphosphine; [(S)-2-(diphenylphosphino)-ferrocenyl]methyldi-t-butylphosphine; [(S)-2-(di-p-tolylphosphino)-ferrocenyl]methyldicyclohexylphosphine; [(S)-2-(di-t-butylphosphino)-ferrocenyl]methyldiphenylphosphine; [(R)-2-(bis(3,5-dimethyl-4-methoxyphenyl)phosphino)ferrocenyl]methyldicyclohexylphosphine; [(R)-2-(bis(4-trifluoromethylphenyl)phosphino)ferrocenyl]methyl-di-t-butylphosphine; [(R)-2-(di(3,5-bis-trifluoromethylphenyl)phosphino)-ferrocenyl]methyldi(3,5-dimethylphenyl)phosphine; [(R)-2-(di(3,5-bis-trifluoromethylphenyl)phosphino)ferrocenyl]-methyldicyclohexylphosphine; [(R)-2-(di-(3,5-dimethylphenyl)-phosphino)ferrocenyl]methylbis(3,5-dimethylphenyl)phosphine; [(R)-2-(di-2-furylphosphino)ferrocenyl]methyldi-3,5-xylyl phosphine; [(R)-2-(dicyclohexylphosphino)ferrocenyl]methyldicyclohexylphosphine; [(R)-2-(dicyclohexylphosphino)ferrocenyl]methyldiphenylphosphine; [(R)-2-(dicyclohexylphosphino)ferrocenyl]methyldi-t-butylphosphine; [(R)-2-(diphenylphosphino)ferrocenyl]methyldi(3,5-dimethylphenyl)phosphine; [(R)-2-(diphenylphosphino)ferrocenyl]methyldicyclohexylphosphine; [(R)-2-(diphenylphosphino)ferrocenyl]methyldicyclohexylphosphine; [(R)-2-(diphenylphosphino)ferrocenyl]methyldiphenylphosphine; [(R)-2-(diphenylphosphino)ferrocenyl]methyldi-t-butylphosphine; [(R)-2-(di-p-tolylphosphino)ferrocenyl]methyldicyclohexylphosphine; and [(R)-2-(di-t-butylphosphino)ferrocenyl]methyldiphenylphosphine. 
     
     
       24. A process according to  claim 3 , wherein the compound of formula I is selected from the group consisting of 1-[2-(dicyclohexylphosphino)-ferrocenyl]ethyldi-t-butylphosphine; 1-[2-(diphenylphosphino)ferrocenyl]-ethyldi-t-butylphosphine; (R)-1-[(S)-2-(dicyclohexylphosphino)-ferrocenyl]ethyldi-t-butylphosphine; (R)-1[(S)-2-(diphenylphosphino)-ferrocenyl]ethyldi-t-butylphosphine; (S)-1[(R)-2-(dicyclohexylphosphino)ferrocenyl]ethyldi-t-butylphosphine; and (S)-1-[(R)-2-(diphenylphosphino)ferrocenyl]ethyldi-t-butylphosphine. 
     
     
       25. A process according to  claim 3 , wherein the compound of formula I is 1-[2-(dicyclohexylphosphino)ferrocenyl]ethyldi-t-butylphosphine. 
     
     
       26. A process according to  claim 3 , wherein the compound of formula I is (R)-1-[(S)-2-(dicyclohexylphosphino)ferrocenyl]ethyldi-t-butylphosphine; (S)-1-[(R)-2-(dicyclohexylphosphino)ferrocenyl]ethyldi-t-butylphosphine; or the racemic mixture thereof. 
     
     
       27. A process according to  claim 26 , wherein the ammoniating agent is ammonia. 
     
     
       28. A process according to  claim 27 , wherein the base is sodium t-butoxide. 
     
     
       29. A process according to  claim 26 , wherein the ammoniating agent is an alkali metal amide. 
     
     
       30. A process according to  claim 29 , wherein the ammoniating agent is lithium amide. 
     
     
       31. A process according to  claim 27 , wherein the leaving group is selected from the group consisting of chloride, bromide, and iodide. 
     
     
       32. A process according to  claim 28 , wherein the leaving group is selected from the group consisting of chloride, bromide, and iodide. 
     
     
       33. A process according to  claim 29 , wherein the leaving group is selected from the group consisting of chloride, bromide, and iodide. 
     
     
       34. A process according to  claim 30 , wherein the leaving group is selected from the group consisting of chloride, bromide, and iodide. 
     
     
       35. A composition comprising:
 (a) an ammoniating agent selected from the group consisting of:
 (i) ammonia; and 
 (ii) a metal amide; and 
 
 (b) a complex comprising:
 (i) a Group VIII metal atom or ion; and 
 (ii) a ligand, wherein the ligand is a compound of formula I: 
 
 
       
         
           
           
               
               
           
         
       
       wherein:
 R 1  and R 2  are independently selected from the group consisting of (C 1 -C 12 )alkyl, (C 1 -C  12 )hetero alkyl, and optionally substituted aromatic rings, or —PR 1 R 2  is a radical of the formula II: 
 
       
         
           
           
               
               
           
         
         wherein α and β are optionally substituted aromatic rings; 
         R 3  and R 4  are independently selected from the group consisting of (C 1 -C 12 )alkyl, (C 1 -C 12 )heteroalkyl, and optionally substituted aromatic rings, or —PR 3 R 4  is a radical of the formula II; 
         R 5  is selected from the group consisting of hydrogen, (C 1 -C 8 )alkyl, (C 1 -C 8 )heteroalkyl and optionally substituted aromatic rings, 
         each R 6  is independently selected from the group consisting of hydrogen, and (C 1 -C 4 )alkyl; 
         wherein each of said optionally substituted aromatic rings is either unsubstituted or substituted at any substitutable position with one or more substituents independently selected from the group consisting of (C 1 -C 4 )alkyl, (C 1 -C 4 )heteroalkyl, (C 1 -C 3 ) fluorinated alkyl, —OR 7 , —SR 7 , and NR 7   2 ; 
         each R 7  is independently selected from the group consisting of (C 1 -C 4 )alkyl and (C 1 -C 4 )heteroalkyl, or, within any occurrence of NR 7   2 , independently of any other occurrence of NR 7   2  the two R 7  groups in combination form (C 4 -C 8 )alkylene or (C 4 -C 8 )heteroalkylene; 
         or any one occurrence of R 6 , or any one substitutable position of any one of the groups R 1 , R 2 , R 3 , R 4 , R 5  and R 7 , is a point of attachment, directly or via a tethering group, to a polymer or a solid phase support; 
         provided that when the ammoniating agent is ammonia, the composition further comprises a base. 
       
     
     
       36. A composition according to  claim 35 , wherein the Group VIII metal is selected from the group consisting of nickel, palladium and platinum. 
     
     
       37. A composition according to  claim 35 , wherein the Group VIII metal is palladium. 
     
     
       38. A composition according to  claim 37 , wherein the ammoniating agent is ammonia. 
     
     
       39. A composition according to  claim 38 , wherein the base is selected from the group consisting of alkali metal alkoxides, carbonates, and phosphates. 
     
     
       40. A composition according to  claim 39 , wherein the base is selected from the group consisting of sodium t-butoxide, cesium carbonate, and tribasic potassium phosphate. 
     
     
       41. A composition according to  claim 39 , wherein the base is sodium t-butoxide. 
     
     
       42. A composition according to  claim 37 , wherein the ammoniating agent is a metal amide. 
     
     
       43. A composition according to  claim 42 , wherein the metal amide is an alkali metal amide. 
     
     
       44. A composition according to  claim 43 , further comprising a zinc halide. 
     
     
       45. A composition according to  claim 43 , wherein the alkali metal amide is lithium amide. 
     
     
       46. A composition according to  claim 45 , further comprising zinc chloride. 
     
     
       47. A composition according to  claim 37 , wherein R 6  is other than hydrogen at one or fewer occurrences. 
     
     
       48. A composition according to  claim 47 , wherein each R 6  is hydrogen. 
     
     
       49. A composition according to  claim 47 , wherein R 5  is hydrogen or methyl. 
     
     
       50. A composition according to  claim 48 , wherein R 5  is methyl. 
     
     
       51. A composition according to  claim 47 , wherein each of R 3  and R 4  is independently secondary or tertiary alkyl. 
     
     
       52. A composition according to  claim 49 , wherein each of R 3  and R 4  is independently secondary or tertiary alkyl. 
     
     
       53. A composition according to  claim 51 , wherein each of R 3  and R 4  is tertiary alkyl. 
     
     
       54. A composition according to  claim 53 , wherein each of R 3  and R 4  is t-butyl. 
     
     
       55. A composition according to  claim 37 , wherein the compound according to formula I is selected from the group consisting of 1-[2-(bis(3,5-dimethyl-4-methoxyphenyl)phosphino)ferrocenyl]ethyldicyclohexylphosphine, 1-[2-(bis(4-trifluoromethylphenyl)phosphino)ferrocenyl]ethyl-di-t-butylphosphine; 1-[2-(di(3,5-bis-trifluoromethylphenyl)phosphino)-ferrocenyl]ethyldi(3,5-dimethylphenyl)phosphine; 1-[2-(di(3,5-bis-trifluoromethylphenyl)phosphino)ferrocenyl]ethyldicyclohexylphosphine; 1-[2-(di-(3,5-dimethylphenyl)phosphino)ferrocenyl]ethylbis(3,5-dimethylphenyl)phosphine; 1-[2-(di-2-furylphosphino)ferrocenyl]ethyldi-3,5-xylyl phosphine; 1-[2-(dicyclohexylphosphino)ferrocenyl]-ethyldicyclohexylphosphine; 1-[2-(dicyclohexylphosphino)ferrocenyl]-ethyldiphenylphosphine; 1-[2-(dicyclohexylphosphino)ferrocenyl]ethyldi-t-butylphosphine; 1-[2-(diphenylphosphino)ferrocenyl]ethyldi(3,5-dimethylphenyl)phosphine; 1-[2-(diphenylphosphino)ferrocenyl]-ethyldicyclohexylphosphine; 1-[2-(diphenylphosphino)ferrocenyl]-ethyldicyclohexylphosphine; 1-[2-(diphenylphosphino)ferrocenyl]-ethyldiphenylphosphine; 1-[2-(diphenylphosphino)ferrocenyl]ethyldi-t-butylphosphine; 1-[2-(di-p-tolylphosphino)ferrocenyl]-ethyldicyclohexylphosphine; 1-[2-(di-t-butylphosphino)ferrocenyl]-ethyldiphenylphosphine.; (R)-1-[(S)-2-(bis(3,5 -dimethyl-4-methoxyphenyl)phosphino)ferrocenyl]ethyldicyclohexylphosphine; (R)-1-[(S)-2-(bis(4-trifluoromethylphenyl)phosphino)ferrocenyl]ethyl-di-t-butylphosphine; (R)-1-[(S)-2-(di(3,5-bis-trifluoromethylphenyl)-phosphino)ferrocenyl]ethyldi(3,5-dimethylphenyl)phosphine ; (R)-1-[(S)-2-(di(3,5-bis-trifluoromethylphenyl)phosphino)ferrocenyl]-ethyldicyclohexylphosphine; (R)-1-[(S)-2-(di-(3,5 -dimethylphenyl)-phosphino)ferrocenyl]ethylbis(3,5-dimethylphenyl)phosphine; (R)-1-[(S)-2-(di-2-furylphosphino)ferrocenyl]ethyldi-3,5-xylyl phosphine; (R)-1-[(S)-2-(dicyclohexylphosphino)ferrocenyl]ethyldicyclohexylphosphine; (R)-1-[(S)-2-(dicyclohexylphosphino)ferrocenyl]ethyldiphenylphosphine; (R)-1-[(S)-2-(dicyclohexylphosphino)ferrocenyl]ethyldi-t-butylphosphine; (R)-1-[(S)-2-(diphenylphosphino)ferrocenyl]ethyldi(3,5-dimethylphenyl)-phosphine; (R)-1-[(S)-2-(diphenylphosphino)ferrocenyl]-ethyldicyclohexylphosphine; (R)-1-[(S)-2-(diphenylphosphino)ferrocenyl]-ethyldicyclohexylphosphine; (R)-1-[(S)-2-(diphenylphosphino)ferrocenyl]-ethyldiphenylphosphine; (R)-1-[(S)-2-(diphenylphosphino)ferrocenyl]-ethyldi-t-butylphosphine; (R)-1-[(S)-2-(di-p-tolylphosphino)ferrocenyl]-ethyldicyclohexylphosphine; (R)-1-[(S)-2-(di-t-butylphosphino)-ferrocenyl]ethyldiphenylphosphine; (S)-1-[(R)-2-(bis(3 ,5-dimethyl-4-methoxyphenyl)phosphino)ferrocenyl]ethyldicyclohexylphosphine; (S)-1-[(R)-2-(bis(4-trifluoromethylphenyl)phosphino)ferrocenyl]ethyl-di-t-butylphosphine; (S)-1-[(R)-2-(di(3,5-bis-trifluoromethylphenyl)-phosphino)ferrocenyl]ethyldi(3,5-dimethylphenyl)phosphine; (S)-1-[(R)-2-(di(3,5-bis-trifl uoromethylphenyl)phosphino)ferrocenyl]-ethyldicyclohexylphosphine; (S)-1-[(R)-2-(di-(3,5-dimethylphenyl)-phosphino)ferrocenyl]ethylbis(3,5-dimethylphenyl)phosphine; (S)-1-[(R)-2-(di-2-furylphosphino)ferrocenyl]ethyldi-3,5-xylyl phosphine; (S)-1-[(R)-2-(dicyclohexylphosphino)ferrocenyl]ethyldicyclohexylphosphine; (S)-1-[(R)-2-(dicyclohexylphosphino)ferrocenyl]ethyldiphenylphosphine; (S)-1-[(R)-2-(dicyclohexylphosphino)ferrocenyl]ethyldi-t-butylphosphine; (S)-1-[(R)-2-(diphenylphosphi no)ferrocenyl]ethyldi(3,5-dimethylphenyl)-phosphine; (S)-1-[(R)-2-(diphenylphosphino)ferrocenyl]-ethyldicyclohexylphosphine; (S)-1-[(R)-2-(diphenylphosphino)ferrocenyl]-ethyldicyclohexylphosphine; (S)-1-[(R)-2-(diphenylphosphino)ferrocenyl]-ethyldiphenylphosphine; (S)-1-[(R)-2-(diphenylphosphino)ferrocenyl]-ethyldi-t-butylphosphine; (S)-1-[(R)-2-(di-p-tolylpho sphino)ferrocenyl]-ethyldicyclohexylphosphine; and (S)-1-[(R)-2-(di-t-butylphosphino)-ferrocenyl]ethyldiphenylphosphine. 
     
     
       56. A composition according to  claim 37 , wherein the compound of formula I is selected from the group consisting of [2-(bis(3,5-dimethyl-4-methoxyphenyl)phosphino)ferrocenyl]methyldicyclohexylphosphine, [2-(bis(4-trifluoromethylphenyl)phosphino)ferrocenyl]methyl-di-t-butylphosphine; [2-(di(3,5-bis-trifluoromethylphenyl)phosphino)-ferrocenyl]methyldi(3,5-dimethylphenyl)phosphine; [2 -(di(3,5-bis-trifluoromethylphenyl)phosphino)ferrocenyl]-methyldicyclohexylphosphine; [2-(di-(3,5-dimethylphenyl)phosphino)-ferrocenyl]methylbis(3,5-dimethylphenyl)phosphine; [2-(di-2-furylphosphino)ferrocenyl]ethyldi-3,5-xylyl phosphine; [2 -(dicyclohexylphosphino)ferrocenyl]methyldicyclohexylphosphine; [2 -(dicyclohexylphosphino)ferrocenyl]methyldiphenylphosphine; [2-(dicyclohexylphosphino)ferrocenyl]methyldi-t-butylphosphine; [2-(diphenylphosphino)ferrocenyl]methyldi(3,5-dimethylphenyl)phosphine; [2-(diphenylphosphino)ferrocenyl]methyldicyclohexylphosphine; [2 -(diphenylphosphino)ferrocenyl]methyldicyclohexylphosphine; [2 -(diphenylphosphino)ferrocenyl]methyldiphenylphosphine; [2-(diphenylphosphino)ferrocenyl]methyldi-t-butylphosphine; [2-(di-p-tolylphosphino)ferrocenyl]methyldicyclohexylphosphine; [2-(di-t-butylphosphino)ferrocenyl]methyldiphenylphosphine.; [(S)-2-(bis(3,5 -dimethyl-4-methoxyphenyl)phosphino)ferrocenyl]-methyldicyclohexylphosphine; [(S)-2-(bis(4-trifluoromethylphenyl)-phosphino)ferrocenyl]methyl-di-t-butylphosphine; [(S)-2-(di(3,5-bis-trifluoromethylphenyl)phosphino)ferrocenyl]methyldi(3 ,5 -dimethylphenyl)phosphine; [(S)-2-(di(3,5-bis-trifluoromethylphenyl)-phosphino)ferrocenyl]methyldicyclohexylphosphine; [(S)-2-(di-(3,5-dimethylphenyl)phosphino)ferrocenyl]methylbis(3,5-dimethylphenyl)-phosphine; [(S)-2-(di-2-furylphosphino)ferrocenyl]methyldi-3,5-xylyl phosphine; [(S)-2-(dicyclohexylphosphino)ferrocenyl]-methyldicyclohexylphosphine; [(S)-2-(dicyclohexylphosphino)ferrocenyl]-methyldiphenylphosphine; [(S)-2-(dicyclohexylphosphino)ferrocenyl]-methyldi-t-butylphosphine; [(S)-2-(diphenylphosphino)ferrocenyl]-methyldi(3,5-dimethylphenyl)phosphine; [(S)-2-(diphenylphosphino)-ferrocenyl]methyldicyclohexylphosphine; [(S)-2-(diphenylphosphino)-ferrocenyl]methyldicyclohexylphosphine; [(S)-2-(diphenylphosphino)-ferrocenyl]methyldiphenylphosphine; [(S)-2-(diphenylphosphino)-ferrocenyl]methyldi-t-butylphosphine; [(S)-2-(di-p-tolylphosphino)-ferrocenyl]methyldicyclohexylphosphine; [(S)-2-(di-t-butylphosphino)-ferrocenyl]methyldiphenylpho sphine; [(R)-2-(bis(3,5-dimethyl-4-methoxyphenyl)phosphino)ferrocenyl]methyldicyclohexylphosphine; [(R)-2-(bis(4-trifluoromethylphenyl)phosphino)ferrocenyl]methyl-di-t-butylphosphine; [(R)-2-(di(3,5-bis-trifluoromethylphenyl)phosphino)-ferrocenyl]methyldi(3 ,5-dimethylphenyl)phosphine; [(R)-2-(di(3,5-bis-trifluoromethylphenyl)phosphino)ferrocenyl]-methyldicyclohexylphosphine; [(R)-2-(di-(3,5-dimethylphenyl)-phosphino)ferrocenyl]methylbis(3,5-dimethylphenyl)phosphine; [(R)-2-(di-2-furylphosphino)ferrocenyl]methyldi-3,5-xylyl phosphine; [(R)-2-(dicyclohexylphosphino)ferrocenyl]methyldicyclohexylphosphine; [(R)-2-(dicyclohexylphosphino)ferrocenyl]methyldiphenylphosphine; [(R)-2-(dicyclohexylphosphino)ferrocenyl]methyldi-t-butylpho sphine; [(R)-2-(diphenylphosphino)ferrocenyl ]methyldi(3,5-dimethylphenyl)phosphine; [(R)-2-(diphenylphosphino)ferrocenyl]methyldicyclohexylphosphine; [(R)-2-(diphenylphosphino)ferrocenyl]methyldicyclohexylphosphine; [(R)-2-(diphenylphosphino)ferrocenyl]methyldiphenylphosphine; [(R)-2-(diphenylphosphino)ferrocenyl]methyldi-t-butylphosphine; [(R)-2-(di-p-tolyphosphino)ferrocenyl]methyldicyclohexylphosphine; and [(R)-2-(di-t-butylphosphino)ferrocenyl]methyldiphenylphosphine. 
     
     
       57. A composition according to  claim 37 , wherein the compound of formula I is selected from the group consisting of 1-[2-(dicyclohexylphosphino)-ferrocenyl]ethyldi-t-butylphosphine; 1-[2-(diphenylphosphino)ferrocenyl]-ethyldi-t-butylphosphine; (R)-1-[(S)-2-(dicyclohexylphosphino)-ferrocenyl]ethyldi-t-butylphosphine; (R)-1-[(S)-2-(diphenylphosphino)-ferrocenyl]ethyldi-t-butylphosphine; (S)-1-[(R)-2-(dicyclohexylphosphino)ferrocenyl]ethyldi-t-butylphosphine; and (S)-1-[(R)-2-(diphenylphosphino)ferrocenyl]ethyldi-t-butylpho sphine. 
     
     
       58. A composition according to  claim 37 , wherein the compound of formula I is 1-[2-(dicyclohexylphosphino)ferrocenyl]ethyldi-t-butylphosphine. 
     
     
       59. A composition according to  claim 37 , wherein the compound of formula I is (R)-1-[(S)-2-(dicyclohexylphosphino)ferrocenyl]ethyldi-t-butylphosphine; (S)-1-[(R)-2-(dicyclohexylphosphino)ferrocenyl]ethyldi-t-butylphosphine; or the racemic mixture thereof. 
     
     
       60. A composition according to  claim 59 , wherein the ammoniating agent is ammonia. 
     
     
       61. A composition according to  claim 60 , wherein the base is sodium t-butoxide. 
     
     
       62. A composition according to  claim 59 , wherein the ammoniating agent is an alkali metal amide. 
     
     
       63. A composition according to  claim 62 , wherein the ammoniating agent is lithium amide. 
     
     
       64. A transition metal complex according to the formula IV: 
       
         
           
           
               
               
           
         
       
       wherein:
 M comprises a Group VIII metal atom or ion; 
 Ar represents a moiety comprising an aromatic ring wherein a carbon atom of the aromatic ring is sigma-bonded to the Group VIII metal atom or ion of M; 
 R 1  and R 2  are independently selected from the group consisting of (C 1  -C 12 )alkyl, (C 1  -C 12 )heteroalkyl, and optionally substituted aromatic rings, or —PR 1 R 2  is a radical of the formula II: 
 
       
         
           
           
               
               
           
         
         wherein α and β are optionally substituted aromatic rings; 
         R 3  and R 4  are independently selected from the group consisting of (C i -C 12 )alkyl, (C 1  -C 12 )hetero alkyl, and optionally substituted aromatic rings, or —PR 3 R 4  is a radical of the formula II; 
         R 5  is selected from the group consisting of hydrogen, (C 1 -C 8 )alkyl, (C 1 -C 8 )heteroalkyl and optionally substituted aromatic rings, 
         each R 6  is independently selected from the group consisting of hydrogen, and (C 1 -C 4 )alkyl; 
         wherein each of said optionally substituted aromatic rings is either unsubstituted or substituted at any substitutable position with one or more substituents independently selected from the group consisting of (C 1 -C 4 )alkyl, (C 1 -C 4 )heteroalkyl, (C 1 -C 3 ) fluorinated alkyl, —OR, —SR 7 , and NR 7   2 ; 
         each R 7 is independently selected from the group consisting of (C 1 -C 4 )alkyl and (C 1 -C 4 )heteroalkyl, or, within any occurrence of NR 7   2 , independently of any other occurrence of NR 7   2  the two R 7  groups in combination form (C 4 -C 8 )alkylene or (C 4 -C 8 )heteroalkylene; 
         or any one occurrence of R 6 , or any one substitutable position of any one of the groups R 1 , R 2 , R 3 , R 4 , R 5  and R 7 , is a point of attachment, directly or via a tethering group, to a polymer or a solid phase support. 
       
     
     
       65. A transition metal complex according to  claim 64 , wherein the Group VIII metal is selected from the group consisting of nickel, palladium, and platinum. 
     
     
       66. A transition metal complex according to  claim 64 , wherein the Group VIII metal is palladium. 
     
     
       67. A transition metal complex according to  claim 66 , wherein R 6  is other than hydrogen at one or fewer occurrences. 
     
     
       68. A transition metal complex according to  claim 67 , wherein each R 6  is hydrogen. 
     
     
       69. A transition metal complex according to  claim 67 , wherein R 5  is hydrogen or methyl. 
     
     
       70. A transition metal complex according to  claim 68 , wherein R 5  is methyl. 
     
     
       71. A transition metal complex according to  claim 67 , wherein each of R 3  and R 4  is independently secondary or tertiary alkyl. 
     
     
       72. A transition metal complex according to  claim 70 , wherein each of R 3  and R 4  is independently secondary or tertiary alkyl. 
     
     
       73. A transition metal complex according to  claim 72 , wherein each of R 3  and R 4  is tertiary alkyl. 
     
     
       74. A transition metal complex according to  claim 73 , wherein each of R 3  and R 4  is t-butyl. 
     
     
       75. A transition metal complex according to  claim 66  comprising a ligand selected from the group consisting of 1-[2-(bis(3,5-dimethyl-4-methoxyphenyephosphino)ferrocenyl]ethyldicyclohexylphosphine, 1-[2-(bis(4-trifluoromethylphenyl)phosphino)ferrocenyl]ethyl-di-t-butylphosphine; 1-[2-di(3,5-bis-trifluoromethylphenyl)phosphino)-ferrocenyl]ethyldi(3,5-dimethylphenyl)phosphine; 1-[2-(di(3,5-bis-trifluoromethylphenyl)phosphino)ferrocenyl]ethyldicyclohexylphosphine; 1-[2-(di-(3,5-dimethylphenyl)phosphino)ferrocenyl]ethylbis(3,5-dimethylphenyl)phosphine; 1-[2-(di-2-furylphosphino)ferrocenyl]ethyldi-3,5-xylyl phosphine; 1-[2-(dicyclohexylphosphino)ferrocenyl]-ethyldicyclohexylphosphine; 1-[2-(dicyclohexylphosphino)ferroceny]-ethyldiphenylphosphine; 1-[2-(dicyclohexylphosphino)ferrocenyl]ethyldi-t-butylphosphine; 1-[2-(diphenylphosphino)ferrocenyl]ethyldi(3,5-dimethylphenyl)phosphine; 1-[2-(diphenylphosphino)ferroceny]-ethyldicyclohexylphosphine; 1-[2-(diphenylphosphino)ferrocenyl]-ethyldicyclohexylphosphine; 1-[2-(diphenylphosphino)ferrocenyl]-ethyldiphenylphosphine; 1-[2-(diphenylphosphino)ferrocenyl]ethyldi-t-butylphosphine; 1-[2-(di-p-tolylphosphino)ferrocenyl]-ethyldicyclohexylphosphine; 1-[2-(di-t-butylphosphino)ferrocenyl]-ethyldiphenylphosphine.; (R)-1-[(S)-2-(bis(3,5-dimethyl-4-methoxyphenyl)phosphino)ferrocenyl]ethyldicyclohexylphosphine; (R)-1-[(S)-2-(bis(4-trifluoromethylphenyephosphino)ferrocenyl]ethyl-di-t-butylphosphine; (R)-1-[(S)-2-(di(3,5-bis-trifluoromethylphenyl)-phosphino)ferrocenyl]ethyldi(3,5-dimethylphenyl)phosphine; (R)-1-[(S)-2-(di(3,5-bis-trifluoromethylphenyephosphino)ferrocenyl]-ethyldicyclohexylphosphine; (R)-1-[(S)-2-(di-(3,5-dimethylphenyl)-phosphino)ferrocenyl]ethylbis(3,5-dimethylphenyl)phosphine; (R)-1-[(S)-2-(di-2-furylphosphino)ferrocenyl]ethyldi-3,5-xylyl phosphine; (R)-1-[(S)-2-(dicyclohexylphosphino)ferrocenyl]ethyldicyclohexylphosphine; (R)-1-[(S)-2-(dicyclohexylphosphino)ferrocenyl]ethyldiphenylphosphine; (R)-1-[(S)-2-(dicyclohexylphosphino)ferrocenyl]ethyldi-t-butylphosphine; (R)-1-[(S)-2-(diphenylphosphino)ferrocenyl]ethyldi(3,5-dimethylphenyl)-phosphine; (R)-1-[(S)-2-(diphenylphosphino)ferrocenyl]-ethyldicyclohexylphosphine; (R)-1-[(S)-2-(diphenylphosphino)ferrocenyl]-ethyldicyclohexylphosphine; (R)-1-[(S)-2-(diphenylphosphino)ferrocenyl]-ethyldiphenylphosphine; (R)-1-[(S)-2-(diphenylphosphino)ferrocenyl]-ethyldi-t-butylphosphine; (R)-1-[(S)-2-(di-p-tolylphosphino)ferrocenyl]-ethyldicyclohexylphosphine; (R)-1-[(S)-2-(di-t-butylphosphino)-ferrocenyl]ethyldiphenylphosphine; (S)-1-[(R)-2-(bis(3,5-dimethyl-4-methoxyphenyl)phosphino)ferrocenyl]ethyldicyclohexylphosphine; (S)-1-[(R)-2-(bis(4-trifluoromethylphenyl)phosphino)ferrocenyl]ethyl-di-t-butylphosphine; (S)-1-[(R)-2-(di(3,5-bis-trifluoromethylphenyl)-phosphino)ferrocenyl]ethyldi(3,5-dimethylphenyl)phosphine; (S)-1-[(R)-2-(di(3,5-bis-trifluoromethylphenyl)phosphino)ferrocenyl]-ethyldicyclohexylphosphine; (S)-1-[(R)-2-(di-(3,5-dimethylphenyl)-phosphino)ferrocenyl]ethylbis(3,5 -dimethylphenyl)phosphine; (S)-1- [(R)-2-(di-2-furylphosphino)ferrocenyl]ethyldi-3,5-xylyl phosphine; (S)-1[(R)-2-(dicyclohexylphosphino)ferrocenyl]ethyldicyclohexylphosphine; (S)-1-[(R)-2-(dicyclohexylphosphino)ferrocenyl]ethyldiphenylphosphine; (S)-1-[(R)-2-(dicyclohexylphosphino)ferrocenyl]ethyldi-t-butylphosphine; (S)-1-[(R)-2-(diphenylphosphino)ferrocenyl]ethyldi(3,5-dimethylphenyl)-phosphine; (S)-1-[(R)-2-(diphenylphosphino)ferrocenyl]-ethyldicyclohexylphosphine; (S)-1-[(R)-2-(diphenylphosphino)ferrocenyl]-ethyldicyclohexylphosphine; (S)-1-[(R)-2-(diphenylphosphino)ferrocenyl]-ethyldiphenylphosphine; (S)-1-[(R)-2-(diphenylphosphino)ferrocenyl]-ethyldi-t-butylphosphine; (S)-1-[(R)-2-(di-p-tolylphosphino)ferrocenyl]-ethyldicyclohexylphosphine; and (S)-1-[(R)-2-(di-t-butylphosphino)-ferrocenyl]ethyldiphenylphosphine. 
     
     
       76. A transition metal complex according to  claim 66  comprising a ligand selected from the group consisting of [2-(bis(3,5-dimethyl-4-methoxyphenyl)phosphino)ferrocenyl]methyldicyclohexylphosphine, [2-(bis(4-trifluoromethylphenyl)phosphino)ferrocenyl]methyl-di-t-butylphosphine; [2-(di(3,5-bis-trifluoromethylphenyl)phosphino)-ferrocenyl]methyldi(3,5-dimethylphenyl)phosphine; [2-(di(3,5-bis-trifluoromethylphenyl)phosphino)ferrocenyl]-methyldicyclohexylphosphine; [2-(di-(3,5-dimethylphenyl)phosphino)-ferrocenyl]methylbis(3,5-dimethylphenyl)phosphine; [2-(di-2-furyphosphino)ferrocenyl]ethyldi-3,5-xylyl phosphine; [2-(dicyclohexylphosphino)ferrocenyl]methyldicyclohexylphosphine; [2-(dicyclohexylphosphino)ferrocenyl]methyldiphenylphosphine; [2-(dicyclohexylphosphino)ferrocenyl]methyldi-t-butylphosphine; [2-(diphenylphosphino)ferrocenyl]methyldi(3,5-dimethylphenyl)phosphine; [2-(diphenylphosphino)ferrocenyl]methyldicyclohexylphosphine; [2-(diphenylphosphino)ferrocenyl]methyldicyclohexylphosphine; [2-(diphenylphosphino)ferrocenyl]methyldiphenylphosphine; [2-(diphenylphosphino)ferrocenyl]methyldi-t-butylphosphine; [2-(di-p-tolylphosphino)ferrocenyl]methyldicyclohexylphosphine; [2-(di-t-butylphosphino)ferrocenyl]methyldiphenylphosphine.; [(S)-2-(bis(3,5-dimethyl-4-methoxyphenyl)phosphino)ferrocenyl]-methyldicyclohexylphosphine; [(S)-2-(bis(4-trifluoromethylphenyl)-phosphino)ferrocenyl]methyl-di-t-butylphosphine; [(S)-2-(di(3,5-bis-trifluoromethylphenyl)phosphino)ferrocenyl]methyldi-3,5-dimethylphenyl)phosphine; [(S)-2-(di(3,5-bis-trifluoromethylphenyl)-phosphino)ferrocenyl]methyldicyclohexylphosphine; [(S)-2-(di-(3,5-dimethylphenyl)phosphino)ferrocenyl]methylbis(3,5-dimethylphenyl)-phosphine; [(S)-2-(di-2-furylphosphino)ferrocenyl]methyldi-3,5-xylyl phosphine; [(S)-2-(dicyclohexylphosphino)ferrocenyl]-methyldicyclohexylphosphine; [(S)-2-(dicyclohexylphosphino)ferrocenyl]-methyldiphenylphosphine; [(S)-2-(dicyclohexylphosphino)ferrocenyl]-methyldi-t-butylphosphine; [(S)-2-(diphenylphosphino)ferrocenyl]-methyldi(3,5-dimethylphenyl)phosphine; [(S)-2-(diphenylphosphino)-ferrocenyl]methyldicyclohexylphosphine; [(S)-2-(diphenylphosphino)-ferrocenyl]methyldicyclohexylphosphine; [(S)-2-(diphenylphosphino)-ferrocenyl]methyldiphenylphosphine; [(S)-2-(diphenylphosphino)-ferrocenyl]methyldi-t-butylphosphine; [(S)-2-(di-p-tolylphosphino)-ferrocenyl]methyldicyclohexylphosphine; [(S)-2-(di-t-butylphosphino)-ferrocenyl]methyldiphenylphosphine; [(R)-2-(bis(3,5-dimethyl-4-methoxyphenyl)phosphino)ferrocenyl]methyldicyclohexylphosphine; [(R)-2-(bis(4-trifluoromethylphenyl)phosphino)ferrocenyl]methyl-di-t-butylphosphine; [(R)-2-(di(3,5-bis-trifluoromethylphenyl)phosphino)-ferrocenyl]methyldi(3,5-dimethylphenyl)phosphine; [(R)-2-(di(3,5-bis-trifluoromethylphenyl)phosphino)ferrocenyl]-methyldicyclohexylphosphine; [(R)-2-(di-(3,5-dimethylphenyl)-phosphino)ferrocenyl]methylbis(3,5-dimethylphenyl)phosphine; [(R)-2-(di-2-furylphosphino)ferrocenyl]methyldi-3,5-xylyl phosphine; [(R)-2-(dicyclohexylphosphino)ferrocenyl]methyldicyclohexylphosphine; [(R)-2-(dicyclohexylphosphino)ferrocenyl]methyldiphenylphosphine; [(R)-2-(dicyclohexylphosphino)ferrocenyl]methyldi-t-butylphosphine; [(R)-2-(diphenylphosphino)ferrocenyl]methyldi(3,5-dimethylphenyl)phosphine; [(R)-2-(diphenylphosphino)ferrocenyl]methyldicyclohexylphosphine; [(R)-2-(diphenylphosphino)ferrocenyl]methyldicyclohexylphosphine; [(R)-2-(diphenylphosphino)ferrocenyl]methyldiphenylphosphine; [(R)-2-(diphenylphosphino)ferrocenyl]methyldi-t-butylphosphine; [(R)-2-(di-p-tolylphosphino)ferrocenyl]methyldicyclohexylphosphine; and [(R)-2-(di-t-butylphosphino)ferrocenyl]methyldiphenylphosphine. 
     
     
       77. A transition metal complex according to  claim 66  comprising a ligand selected from the group consisting of 1-[2-(dicyclohexylphosphino)-ferrocenyl]ethyldi-t-butylphosphine; 1-[2-(diphenylphosphino)ferrocenyl]-ethyldi-t-butylphosphine; (R)-1-[(S)-2-(dicyclohexylphosphino)-ferrocenyl]ethyldi-t-butylphosphine; (R)-1-[(S)-2-(diphenylphosphino)-ferrocenyl]ethyldi-t-butylphosphine; (S)-1-[(R)-2-(dicyclohexylphosphino)ferrocenyl]ethyldi-t-butylphosphine; and (S)-1-[(R)-2-(diphenylphosphino)ferrocenyl]ethyldi-t-butylphosphine. 
     
     
       78. A transition metal complex according to  claim 66  comprising a ligand which is 1-[2-(dicyclohexylphosphino)ferrocenyl]ethyldi-t-butylphosphine. 
     
     
       79. A transition metal complex according to  claim 66  comprising a ligand which is (R)-1-[(S)-2-(dicyclohexylphosphino)ferrocenyl]ethyldi-t-butylphosphine; or (S)-1-[(R)-2-(dicyclohexylphosphino)ferrocenyl]ethyldi-t-butylphosphine.